Theory of femtosecond coherent double-pump single-molecule spectroscopy: Application to light harvesting complexes

Journal Article · Tue Apr 28 04:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4919240· OSTI ID:22415698

Chen, Lipeng; Zhao, Yang ^[1]; Gelin, Maxim F.; Domcke, Wolfgang ^[2]

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1. Division of Materials Science, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798 (Singapore)
2. Department of Chemistry, Technische Universität München, Garching D-85747 (Germany)

We develop a first principles theoretical description of femtosecond double-pump single-molecule signals of molecular aggregates. We incorporate all singly excited electronic states and vibrational modes with significant exciton-phonon coupling into a system Hamiltonian and treat the ensuing system dynamics within the Davydov D{sub 1} Ansatz. The remaining intra- and inter-molecular vibrational modes are treated as a heat bath and their effect is accounted for through lineshape functions. We apply our theory to simulate single-molecule signals of the light harvesting complex II. The calculated signals exhibit pronounced oscillations of mixed electron-vibrational (vibronic) origin. Their periods decrease with decreasing exciton-phonon coupling.

• OSTI ID: 22415698
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 16 Vol. 142; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
COMPLEXES
COUPLING
ELECTRONS
EXCITONS
HAMILTONIANS
MOLECULES
OSCILLATIONS
PHONONS
SPECTROSCOPY
VISIBLE RADIATION